Ivantsova Natalia A, Kuzin Eugene N, Kuznetsov Vitaly V, Filatova Elena A, Pirogov Andrey V, Timchenko Yury V, Poineau Frederic, German Konstantin E, Averina Yulia M, Kolesnikov Artem V
D. I. Mendeleev University of Chemical Technology of Russia Moscow 125047 Russian Federation.
A. N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences 119071 Moscow Russian Federation.
RSC Adv. 2025 Jun 25;15(27):21785-21793. doi: 10.1039/d5ra02632f. eCollection 2025 Jun 23.
The electrochemical mineralization of tetracycline in chloride aqueous solutions using Pt/Ti anodes has been investigated. The mineralization process, oxidation efficiencies and oxidation products were characterized by UV-visible spectroscopy and HPLC-MS. Tetracycline oxidation efficiencies are 97 ± 2% in 0.64 wt% HCl and 85 ± 3% in 0.64 wt% NaCl within 15 minutes of electrolysis. UV-visible spectroscopy confirmed the degradation of the antibiotic's π-conjugated electron system and allowed the identification of active species (, hydrogen peroxide and dissolved chlorine) that can potentially degrade tetracycline. The formation of these active species is due to the high positive potential of the Pt/Ti anode during electrolysis. HPLC-MS studies show the intensity of the tetracycline peak to gradually decrease during electrolysis, indicating its oxidation. Peaks corresponding to oxidation intermediates with a molecular weight above 70 were not detected, which indicates the absence of oxidation products with higher molecular mass. During electrochemical oxidation of tetracycline, small amounts of formaldehyde are formed, but its concentration can be brought to an acceptable level by diluting the solution. In negative mode, chlorate ions were detected in the NaCl solutions, which are likely formed from the stepwise oxidation of chloride ions; however, this phenomenon is not observed in HCl solutions.
研究了使用Pt/Ti阳极在氯化物水溶液中对四环素进行电化学矿化的过程。通过紫外可见光谱和高效液相色谱-质谱联用技术对矿化过程、氧化效率和氧化产物进行了表征。在电解15分钟内，四环素在0.64 wt% HCl中的氧化效率为97±2%，在0.64 wt% NaCl中的氧化效率为85±3%。紫外可见光谱证实了抗生素的π共轭电子体系的降解，并确定了可能降解四环素的活性物种（、过氧化氢和溶解氯）。这些活性物种的形成是由于电解过程中Pt/Ti阳极具有较高的正电位。高效液相色谱-质谱联用研究表明，在电解过程中四环素峰的强度逐渐降低，表明其发生了氧化。未检测到对应分子量高于70的氧化中间体的峰，这表明不存在更高分子量的氧化产物。在四环素的电化学氧化过程中，会形成少量甲醛，但通过稀释溶液可将其浓度降至可接受水平。在负离子模式下，在NaCl溶液中检测到了氯酸根离子，它们可能是由氯离子的逐步氧化形成的；然而，在HCl溶液中未观察到这种现象。
